Polymerization of olefins and the alkylation of polymer



SePf- 30, 1952 J. T. HoREczY u POLYMERIZATION OF' OLEFINS AND THE ALKYLATION OF' POLYMER Filed Dec. e, 195o mor-. 3011 INVENTOR. Jo seph T. Horeczy,

Patented Sept. 30, v 1952 UNITED y STAT-Es mrsmfy ossidi-z POLYll/IERIZATION OF OLEFINS AND THE ALKYLATION OF POLYMER Joseph TgfHorerczy, Baytown, Tex'., assignor, by mesne assignments, to Standard Oil Development. Company, Elizabeth, N. J., a corporation ofDelawarei y Application December 6, 1950, Serial No. 199,515

' L l6 Claims. (C1. 26o- 671) *.The present invention is directed to a method forproducing a non-selective polymer. MoreV particularly, the invention is directed to the nonselective polymerization of oleiins having Scar-- bonatoms inthe molecule. The invention is also concerned with the polymerization of oleiins having 6 carbon atoms in themoleculeand the manufacture of a product'` which'is a rawmaf terial suitable for use inthemanufacture of detergents.

as typed by schmitt and'Boor'd' in the Journai ofthe American Chemicalfso'ciety. volume 5 4,

1o 1 The present invention maybe described briefly as involving the polymerization ofk an olefinic* page 751 (Februaryj1932) ,f having 6 carbon atoms' fin the molecule, atl a temperature in the range between 175 and 225 F. in the presence yof av sulfuric acid polymerizationcatalyst having a titratable acidity no less than '70% H2SO4 under equilibrium conditions of polymerization. Under these conditions, a polymer is produced in high yields. In accordance with the present invention the polymer may be distilledfto recover a fraction containing 12 carbon atomsin the molecule which isthen admixed with an aromatic hydrofcarbon having 6 to`8 carbon atoms in the mole-i oule 4to form a feed mixture which may then be contacted with .an alkylation catalyst .to cause alkylation of the aromatic hydrocarbon with the polymer having 12 ,carbon atoms in the molecule;"the alkylate so formed from the aromatic hydrocarbon and the polymerhaving 12 carbon atomsfin the molecule isasuitable raw material i'or'l thel manufacture yof detergents byv vsuliona tionand subsequent neutralization.l

The olefins forming afeed stock Vof the present inventioninclude the type ,I Ifolens,` such as`v` hexene-l, the type-II olefinsrsuch as cisand.

trans-hexene-2 and`hexene3t he type III olens, such Aas 2 methylpentene-fl. and the type IV oleflns, such as 2 methylpenteneZ.. The feed stock may also include theA type V o1ens havingl 6y carbon atoms in the molecule', vsuch 'as 2,3 -dlmethylbutene-2. The feed stock will `contain also hexanes" 'and may be recovered from 'catalytic processes, suoli as catalytic cracking operations.k The olenic mixture may also be recovered fromv thermal cracking operations or vfrom the product produced' by 'polymerizing thermally""propylene` and ethylene-ff' l"Ihe"c o'ndition's employed inthe polymerization steplof'ftliefpresent invention-'include a tempera`` ture-in the range between l1'75'and' 2255l F., and

a sulfuric' acid catalyst having' a -titratabie -i-,pciartyA tacted with the sulfuricfa'cid catalyst inthe strength mentioned for* a time in the' rangetrbea, tween 30 and 60 minutes. Such conditions give an olefinic conversion in therangefbet'ween about* and 100%.

The Valkylation conditions includeajtempera'- ture inthe range between 309 -and145q F. and? preferably a temperature in the-range `fromto vEl.; the lower temperature limit is'dictatedv` by the choice'of the aromatic hydroc'arbon-ein#v ployed. Thus when benzenei's usedasithe aro-1 matic hydrocarbon it will-bel desirable not to go below"30 F. It will beunderstood that'when'=4 lowerf temperatures in the range given areHem-' ployed', it will be necessary to provide -refrigerav tion facilities. The alkylation catalyst is prefer-il ably aluminum chloride promoted with hydrogen chloride although other Friedel-Crafts'catalysts which are Well known inr their usein alkylatin. reactions may be employed. Thev amountlffof aluminum chloride `used will vary but satisfac-.-.vv `tory results may be obtained with `about 0.3 pound per gallon of alkylate and the amount usedrmay be inthe rangev from'0.1 to about 0.5 pound of aluminum chloride per gallon of alkylate. The'` aluminum chloride may suitablybe promoted The aromatics will be employed with the' ole# fin polymer in a ratio in the range? from 3:-'1-*tof 10:1 with a preferred ratio of about' 5:15'

The invention will be'further illustratedby'- reference to the drawing inw-which the singlev figure'is afiow diagram of a preferredmodeof conducting the invention.

Referring now to the drawing, numeraliv II designates a feed line by way of which anbie-t Iinic mixture having 6 carbonatoms in the melee., cule and containing type I, II, III andv IV olee' fins and hexanes is introduced into the system from a source not shown. The feed in line ll is pumped thereby by pump l2 into a polymerizaf tion zone I3 through gjets or other distributionv means 4I4 to contact` sulfuric acid in zone l31hav ing a titratable `acidity no less 'than '70% I-IzSOi under equilibrium conditions. Statingthis other--v wise, the equilibrium titratableacidity shoul'dbe To' maintain *the* strength` vof the iacid at--tle properrpointf, "ire'e'shf' no less 'than 70% HQLSOJ..

a polymer is formed which is dischargedalongrv f with-some acid from zone I3 by line-I-8finto a settling drum I9 which is of suflicient capacity to allow separation by gravityto -fta'ke I place "between the polymer and the-.aci'dlgcarnied olver: therewith. The recycled acid is withdrawn from neutralization and drying of the neutralized sulfonated product.

The aromatic hydrocarbon employed in the practice of the present invention may be benzene, toluene or xylene. It is preferred, however, to use lbenzene and;A toluene: sinceathesef aromatics allow` the production of? very. des-i'ableY-alkylates for detergent manufacture.

, f, The invention will be illustrated further by the Yfollowing exarriple Vin which a hexene fraction lcontariningftype If-115111 and IV olens, and posseparation zone I9 by line 20,:andzis recycled inj y part byline I6 to linel I5 while'another portion Ii basedon'vthe oleiins was obtained. The polymer may be discharged. t t

The polymer separatedrom the acid in zone Illu-is discharged therefrom by line 2| washed witlr-4 a.suitable neutralizing agent y such... as an g aqueous solutionA of-sodi'umE hydroxide in-means.

noteshownfto Vremove Iacidityandis then introduced'in-toasfractionation zonew22. which may be aeseries vof gfractionating, towers but for conyen-yj iencef fof f description ,is shownr asy a singler` A-iractionating tower.V Fractionating tower 22 is;V providedjw-th ,-suitabler internal f baffling equipment, v

suchasj beligcap; trays, ftd allow intimatergcontact: between -vapors.- ands liquids; and :a1-lows and in:-

Seres# separation-animating several components f oi-fthe-fllydrocarbom feed szhereto.y vF'ractionationl zoneZz-Visprovided withLa heating means ,illus--l trated bycoil: 2'3' rvand-bm 'adjustment Voi temperar;

turefand .fpressure; gtherein allows;y separation..` of:4 hexanes :overheadiby-lneyZ 4- land withdrawal of ,a

light:plymer :by' line-:25.- :gLine' 26. -isprovided -for j removal :of-heavy polymeruwhile the',l desirable..` productv` including-:C12 polymer Yis-withdrawn,from

zone V22=byrrlirle21. .':Line 21vv discharges the C12` polymergmtoganfalkylation zone' 28. vPriorto -en trancefoff-polymer intotvalkylation zone 28 ithasl added-toitfbyline 29 anyaromatic hydrocarbon havingifromr Sto 8 carbonatomszinwthe molecule:

to swhichfisz. added aluminum fchloride introduced bynline 3 0e and i hydrogen chloride .introduced by 1 li-x1."3|-=v--I .fz ,i j, alkylationmzone: 28 'fth'e catalyst.; may Izbez the; `form of'satsludgefof: aluminum ,chloride or. .iti may2 bef'suitably disposed ion .ansupporting nia-tea; rial: Regardless' of-the type or f formof;catalyst:l used-in :alkyl-ation zonef28f, 'conditionsareladjusted' therein-fto-fallow:alkylationv ofthe, aromatic lhy drocarbon'with-,the Cm polymer producedin the; polymerization zone. Alkylation zone' 2 8 is pro` vided ,withfarecyclevfline 32.',which allows the product and unreacted material todischarge back intofIi'neQz-fl. to recycleto the alkyl'ation zone, to, cus'e" substantially completegreaction.ll .Thelprodif uct from alkylation zone' 28 is .,withdrawnjby'line" 33 and'is'"discharged thereby,` after neutralizamatics.' and.recovery-',ftherepf:and withdrawal by);

lineB-l of hea-yy :a'lkylatea y'Iliedesired; :alkylate isftreovered .byz flinerf @and -mayibe gused fonl manufacturerofgdetergents. byombmation Qi. issfwellflslown@theartincladiaasulfqnstia;.

.acidity@73,953l Has@ was employed. This titratable acidity wasln'iaintained by addition of 85% l. H2SQ4 .togthe polymerization zone. Under these conditions apolymer'yield of 70 volume per cent rhe, detersive 'etre my" ofVA misnomer wasgde.

sudsingrcharacteiifstics 'of' the` s ddillimlauliyl l stantially all of the olefins are polymerlzed. For example, in a hexane fraction containing about 57% of olens, 55% of them were Jpolymerized under the foregoing conditions. The conversion of olens was around 97%. It is thought that theA polymer produced under the milder conditions, which allows selective polymerization, undergoes fragmentation'during alkylation to produce low molecular weight alkylate which is unsuitable for detergent manufacture.

The nature and objects of the present invention having been fully described and illustrated, what I desire to claim as new and useful and to secure by Letters Patent is: v

1. A method for polymerizing a mixture of oleflnic hydrocarbons having 6 carbon atoms in the molecule and containing type I. II, III and IV olens and hexanes which comprises contacting said mixture at a temperature in the range between 175 to 225 F. with sulfuric acid having a ttratable acidity no less than 70% I-IzSO.;t under equilibrium conditions to produce an olenic polymer containing twelve carbon atoms in the molecule and recovering said polymer.

2. A method for polymerizing a mixture of olcnic hydrocarbons having 6 carbon atoms in the molecule and containing type I, II, III and IV olefins and hexanes which comprises contacting said mixture at a temperature in the range between 175 and 225 F. with sulfuric acid having a titratable acidity in the range between 70% and 75% II2SO4 under equilibrium conditions for a time in the range between 30 and 60 minutes to convert at least 90% of said olefins and to produce a, polymer having twelve carbon atoms in the molecule and recovering said polymer.

3. A method for producing an alkylate suitable for use in the manufacture of detergent whichv comprises contacting a mixture of olefinic hydrocarbons having 6 carbon atoms in the molecule and containing type I, II, III and IV olefins and hexanes at a temperature in the range between 175 and 225 F. with sulfuric acid having a'titratable acidity no less than 70% H2804 under equilibrium conditions to form a polymerized product,v distilling said product of said able vfor use in the manufacture of detergents which comprises contacting a mixture of oleflnic hydrocarbons having 6 carbon atoms in the molecule and containing type I, II, III and IV volefns and hexanes at a temperature in the range between 175 and 225 F. with sulfuric acid having a titratable acidity in the range between and 75% H2SO4 under equilibrium conditions for a time in the range between 30 and 60 `minutes to convert at least of said olefins.

and to produce a polymerized product, distilling said product -to recover a, polymer having 12 carbon atoms in the molecule, admixing `said polymer with an` aromatic hydrocarbon having from 6 to 8 carbon atoms in the molecule, the volume ratio of aromatics to olefns being in the range of from 3:1 to 10:1, contacting the admixture with a promoted aluminum chloride catalyst at a temperature in the range between 30 and 145 F. in the liquid phase to alkylate said aromatic hydrocarbon with said polymer and to form an alkylate, and recovering said alkylate.

5. A method in accordance with claim 4 ln which thefaromatic hydrocarbon is benzene.

6. A method in accordance with claim 4 in which the aromatic hydrocarbon is toluene.

JOSEPH T. HORECZY.

REFERENCES CITED The following references are of record in the le of this patent:

UNITED STATES PATENTS 

3. A METHOD FOR PRODUCING AN ALKYLATE SUITABLE FOR USE IN THE MANUFACTURE OF DETERGENT WHICH COMPRISES CONTACTING A MIXTURE OF OLEFINIC HYDROCARBONS HAVING 6 CARBON ATOMS IN THE MOLECULE AND CONTAINING TYPE I, II, III, AND IV OLEFINS AND HEXANES AT A TEMPERATURE IN THE RANGE BETWEEN 175* AND 225* F. WITH SULFURIC ACID HAVING A TITRATABLE ACIDITY NO LESS THAN 70% H2SO4 UNDER EQUILIBRIUM CONDITIONS TO FORM A POLYMERIZED PRODUCT, DISTILLING SAID PRODUCT OF SAID OLEFINS TO RECOVER A POLYMER CONTAINING 12 CARBON ATOMS IN THE MOLECULE, ADMIXING THE POLYMER WITH AN AROMATIC HYDROCARBON HAVING 6 TO 8 CARBON ATOMS IN THE MOLECULE, ALKYLATING THE AROMATIC HYDROCARBON IN SAID ADMIXTURE WITH THE OLEFINIC POLYMER TO FORM AN ALKYLATE AND RECOVERING SAID ALKYLATE. 